Hydrometallurgy 74 (2004) 259 – 265

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Beneficiation of a Greek serpentinic nickeliferous ore

Part I. Mineral processing
Stella Agatzini-Leonardou *, Ioannis G. Zafiratos, Dionysios Spathis
Laboratory of Metallurgy, Department of Mining and Metallurgical Engineering, National Technical University of Athens,
9, Ir. Polytechniou Street, Athens 15780 Zografos, Greece
Received 18 February 2004; received in revised form 24 May 2004; accepted 28 May 2004

Abstract

Serpentinic ore, from the ‘‘Kastoria’’ nickeliferous deposit in Northern Greece, was first processed to reject as much of its
calcite content as possible. Partial separation of calcite from the ore was achieved by the use of a strong magnetic field, the
extent of which depended on feed particle size. The losses of nickel in the nonmagnetic product were about 5%, while the
percentage CaO removal was about 37%. Based on the experimental findings, a mineral processing scheme was devised and
applied in order to prepare a suitable sulphuric acid heap or agitation leaching feed.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Nickel laterite ores; Serpentine; Magnetic separation; Autogenous grinding; Calcite removal

1. Introduction This involves prereduction of the ore in rotary kilns,

Greece is the only EU country with extensive but
low-grade nickel laterites. They mainly occur as
limonitic laterites and, to a lesser extent, as serpentinic
laterites. The Greek laterites are unique in the world in
that they are sedimentary and have originated by
transport and sedimentation of laterite-derived mate-
rial, generated by weathering of ultramafic rocks
(Kuhnel et al., 1974; Golightly, 1979; Manceau and
Calas, 1986; Skarpelis et al., 1993; Orphanoudaki et
al., 1997; Boskos et al., 2000).
The Greek limonitic laterites have been exploited
to produce ferronickel via a pyrometallurgical route.
* Corresponding author. Tel.: +30-210-7722234; fax: +30-210-
7722218.
E-mail address: agatzi@metal.ntua.gr (S. Agatzini-Leonardou).
reduction smelting in electric furnaces, and upgrading
of the raw ferronickel in a converter to the final 20 –
25% Ni grade. Because of the rising cost of energy,
the method is economically marginal when ore with
0.95 – 1% nickel is treated and is uneconomic for
lower grade laterites. Direct application of the above
pyrometallurgical method to existing serpentinic lat-
erites is not feasible because the slag produced is
difficult to melt, resulting in higher energy require-
ments and poor phases (metal –slag) separation.
An innovative integrated hydrometallurgical meth-
od for nickel and cobalt extraction from Greek limo-
nitic laterites has been developed and patented
(Agatzini-Leonardou and Dimaki, 1994; Agatzini-
Leonardou and Dimaki, 2001; Agatzini-Leonardou
and Karidakis, 2000; Agatzini-Leonardou et al.,
2000) as a result of many years of work at the

0304-386X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2004.05.005
260 S. Agatzini-Leonardou et al. / Hydrometallurgy 74 (2004) 259–265

Laboratory of Metallurgy of the National Technical Table 1

University of Athens. Chemical analysis of the ‘‘Kastoria’’ ore (bulk sample)
The ‘‘HEap Leach LAteriteS’’ (HELLAS) method Component Percentage (%)
comprises heap leaching of the ore with dilute Ni (NiO) 1.44 (1.83)
sulphuric acid at ambient temperature, purification Co (CoO) 0.05 (0.06)
Fe (Fe2O3) 9.29 (13.29)
of the leach liquor produced by chemical precipita-
Al (Al2O3) 0.37 (0.70)
tion at atmospheric pressure, and recovery of nickel Cr (Cr2O3) 0.57 (0.83)
and cobalt from the purified leach liquor either by Ca (CaO) 12.72 (17.80)
solvent extraction and electrowinning or by chemical Mg (MgO) 7.85 (13.02)
precipitation. Mn (Mn3O4) 0.18 (0.25)
SiO2 21.37
A research project was undertaken to study the
CO2 15.45
application of ‘‘HELLAS’’ to the ‘‘Kastoria’’ serpen- Loss on ignition at 1000 jC 22.06
tinic deposit in Northern Greece (Spathis, 1999). Be-
cause of its relatively high (f18%) calcium oxide
content, the ore had to be first processed in order to The ‘‘Kastoria’’ laterite deposit was formed on
remove as much of its calcite as possible. serpentinised hartzburgite during the Eocene period.
The only known upgrading process presently The ore appears as a discontinuous layer of sediment
practiced in serpentinic laterite beneficiation plants deposited on serpentinised ultramafic rock, which rep-
around the world is rock rejection. Laterite ores often resents relics of old weathering crust (Skarpelis et al.,
contain boulders that may be barren of nickel. These 1993). The sample was analysed mineralogically in
boulders are typically surrounded by very fine, loose- detail by ore microscopy and X-ray diffraction. The
ly adhering nickeliferous material. Since the nickel- mineral chemistry was determined by electron micro-
bearing material is softer than the core of the boulder, probe analysis.
mild abrasion may result in significant upgrading. The Kastoria laterite consists, predominantly, of
This can be done in a ‘‘trommel’’ rock rejection nickeliferous serpentine [Mg3Si2O5(OH)4], nickelifer-
device or in an autogenous grinding drum. In both ous magnesian-cronstedtite, calcite, and quartz. Goe-
cases, the barren cores can be washed and screened thite, hematite, saponite [(Ca, Na)0.66Mg6(Si7.34Al0.66)
out (Queneau and Weir, 1986). On the Island of New O20(OH)4. nH2O], chromite, talc [Mg6Si8O20(OH)4],
Caledonia, Societie Le Nickel sorts out the peridotitic and tremolite [Ca2Mg5Si8O22(OH)2] are present in
rock (15 – 20% of the mine output) from the serpen- small amounts.
tinic ore by means of a revolving screen, called Serpentine is the most important mineral. In some
Tritout, which is a heated trommel (Testut and places it is replaced by cronstedtite [(Fe2 +8Fe3 +4)
Raffinot, 1985; Pelletier, 1996). The Moa Bay plant, (Si4Fe3 +4)O20(OH)16], an iron-rich sheet silicate min-
in Cuba, uses water scrubbing in a trommel for rock eral. Calcite appears as a vein mineral as well as in
rejection (Dufour, 1985). small pockets within the serpentine matrix making it
Within the framework of the research project con- very difficult to separate from the ore. Quartz aggre-
ducted for the ‘‘Kastoria’’ deposit, a magnetic sepa- gates, pseudo-morphically replacing serpentine, to
ration process, not previously evaluated for this type some extent, are often associated with calcite. The
of ore, was applied and the results are given in the quartz aggregates commonly occur as small pockets in
present paper. the matrix of serpentine.
The goethite content in the ore is approximately
5%. Goethite appears in veinlets or in small grains
2. Materials and methods distributed in the matrix of serpentine. It is more
abundant in places where cronstedtite predominates.
A representative sample of 1.2 t of ‘‘Kastoria’’ ore Chromite occurs in small grains within the matrix of
was received from the ‘‘Kastoria’’ mine in Northern serpentine and cronstedtite. Its content is about 1%.
Greece, crushed to 50 mm. Its chemical analysis is Small amounts of chlorite, saponite, talc flakes, and
given in Table 1. tremolite are also present.
 S. Agatzini-Leonardou et al. / Hydrometallurgy 74 (2004) 259–265 261

Table 2 Table 3
Size analysis of the ‘‘Kastoria’’ ore Size analysis of the ‘‘Kastoria’’ magnetic separation feed
Particle size (mm) Weight on screen (g) Percentage Particle size (mm) Weight on screen (kg) Weight (%)
50 + 25 957.7 19.71 50 + 10 9.04 28.6
25 + 19 270.4 5.57 10 + 4 5.24 16.6
19 + 12.7 498.3 10.26 4+2 4.05 12.8
12.7 + 9.5 198.1 4.08 2+1 2.83 8.9
9.5 + 6.8 340.9 7.02 1 10.47 33.1
6.8 + 4.75 108.3 2.23 Total 31.63 100.00
4.75 + 2 703.2 14.48
2+1 443.9 9.14
1 + 0.5 420.9 8.66
0.5 + 0.15 589.3 12.13 content of the ore is limited, given their small relative
0.15 326.8 6.73 amounts.
Total 4857.8 100.00
As previously described, the above mineralogical
analysis indicated that the main nickeliferous minerals
were serpentine and cronstedtite while the main
The microprobe analysis showed that the minerals gangue minerals were quartz and calcite. Taking into
serpentine and cronstedtite constitute the main nickel consideration that nickeliferous minerals such as
carriers in the ‘‘Kastoria’’ ore. More specifically, the garnierite, limonite, and serpentine are slightly mag-
NiO content in serpentine ranges from 0.98% to netic, while quartz and calcite are nonmagnetic, only
6.38%, with a mean value from 20 analyses of a high intensity magnetic field would achieve their
3.44%. The NiO content in cronstedtite ranges from separation. This requires the use of high gradient
2.78% to 11.5%, averaging 5.86%. Saponite, goethite, magnetic separators (HGMS). Such a separation
and hematite are also nickeliferous minerals, contain- would be effective provided that an adequate degree
ing on the average 1.6%, 1.3%, and 1.8% NiO, of mineral liberation has been previously achieved by
respectively; however, their contribution to the nickel grinding. Considering that a large fraction of fines in

Fig. 1. Distribution of chemical constituents in the particle size fractions of the ‘‘Kastoria’’ ore.
262 S. Agatzini-Leonardou et al. / Hydrometallurgy 74 (2004) 259–265

Table 4 Table 5
Size analysis of the ‘‘Kastoria’’ autogenous grinding product Results of autogenous grinding tests on the 50 + 10 mm size
Particle size (mm) Weight on screen (kg) Weight (%) fraction of the ‘‘Kastoria’’ ore

50 + 10 5.15 57.0 Particle 50 + 10 10 + 4 4+2 2+1 1 Feed

10 + 4 0.75 8.3 size (mm)
4+2 0.21 2.3 wt.% 57 8.3 2.3 1.2 31.2 100
2+1 0.11 1.2 Fe2O3 7.04 8.04 8.46 9.47 13.47 9.19
1 2.82 31.2 Ni 0.96 1.05 0.54 0.57 2.00 1.28
Total 9.04 100.00 Co 0.03 0.04 0.04 0.04 0.07 0.04
SiO2 37.65 32.52 34.23 32.95 29.09 34.42
CaO 23.09 23.65 22.31 21.27 18.39 21.63
the ore is not preferable for heap leaching, determi- MgO 9.62 9.79 9.62 10.28 14.10 11.04
ning the coarsest size fraction of ore, for which
magnetic separation is effective, was a major goal
The results of the chemical analysis of the ore size
of this study.
fractions are given in Fig. 1.
An amount of 600 kg from the initial ‘‘Kastoria’’
The rest of the 36.5-kg sample (31.6 kg) was
ore sample was homogenized in a mixing drum and
screened, using 10-, 4-, 2-, and 1-mm sieves, for
divided by the ‘‘cross’’ method and homogenization to
processing by different magnetic separators available
give subsamples of 150 kg and subsequently 36.5 kg.
in the laboratory. The size fractions thereby produced
One of the 36.5-kg subsamples was further divided
are given in Table 3.
and a 4.9-kg portion was finally taken for dry size
analysis. The results are shown in Table 2.
A sample of approximately 100 g from each size
3. Results and discussion
fraction was taken, using a Jones riffle splitter, ground
to 100 mesh, and chemically analysed in order to
The 50 + 10 mm size fraction was fed to a
determine which size fractions would either be
rotating autogenous grinding drum in order to effect
rejected, as being barren of nickel and high in calci-
rock rejection, prior to feeding the ore to magnetic
um, or further be processed by magnetic separation.
separators. The product, after 15-min grinding in the
drum and water washing of the coarsest fraction, was
passed through the same as above sieve sizes and the
results are given in Table 4.
The 50 + 10 mm fraction of the autogenous
grinding product was set aside for possible rejection,

Table 6
Results of magnetic separation tests on the 10 + 4 mm size
fraction of the ‘‘Kastoria’’ ore
Material Magnetic Nonmagnetic Feed
product product
wt.% 64.9 35.1 100
Ni 1.70 1.07 1.48
CaO 16.09 25.47 19.38

Material Ni units Ni CaO CaO

distribution units distribution
(%) (%)
Magnetic 1.10 74.32 10.44 53.87
Nonmagnetic 0.38 25.68 8.94 46.13
Fig. 2. Variation of Ni/CaO ratio with particle size in the serpentinic
Feed 100.00 100.00
run-of-mine ‘‘Kastoria’’ ore.
 S. Agatzini-Leonardou et al. / Hydrometallurgy 74 (2004) 259–265 263

Table 7 Table 9
Results of magnetic separation tests on the 4 + 2 mm size fraction Results of magnetic separation tests on the 2 + 1 mm size fraction
of the ‘‘Kastoria’’ ore of the ‘‘Kastoria’’ ore (low field intensity)
Material Magnetic Nonmagnetic Feed Material Magnetic Nonmagnetic Feed
product product product product
wt.% 82 18 100 wt.% 89.8 10.2 100
Ni 1.69 0.46 1.47 Ni 1.74 0.40 1.60
CaO 13.15 35.35 17.14 CaO 12.26 34.70 14.55

Material Ni units Ni CaO CaO Material Ni units Ni CaO CaO

distribution units distribution distribution units distribution
(%) (%) (%) (%)
Magnetic 1.39 94.56 10.78 62.89 Magnetic 1.56 97.50 11.01 75.67
Nonmagnetic 0.08 5.44 6.36 37.11 Nonmagnetic 0.04 2.50 3.54 24.33
Feed 100.00 100.00 Feed 100.00 100.00

depending on its nickel content, while the other
fractions were added to the respective fractions of
the initial sample for the magnetic separation study.
The 10 + 4 and 4 + 2 mm fractions were fed to a
permanent magnet HGMS machine, while the 1 mm) of the autogenous grinding product contained
and 2 + 1 mm fractions were processed in a variable
intensity magnetic separation device.
As seen in Fig. 2, no fraction of the run-of-mine
ore can be rejected as having a sufficiently low Ni/
CaO ratio. Likewise, only the finest fraction ( 0.15
mm) can be passed on to the leaching stage as having
a significantly high Ni/CaO ratio. However, it was
decided that all fractions should be processed for
calcite rejection prior to leaching. The results of the
autogenous grinding of the ‘‘Kastoria’’ ore are shown
in Table 5, while the magnetic separation results on
various size fractions are presented in Tables 6 –11. A
nickel content of less than 0.5% was targeted for the
material rejected, whereas the lowest possible CaO
content was desirable for the upgraded material.
As seen in Table 5, the coarse fraction ( 50 + 10
0.96% nickel and it could not be rejected. This
fraction was subsequently ground to 10 mm and
added to the magnetic separation feed material. It was
concluded that a feed material of smaller particle size
is necessary for an efficient separation by autogenous
grinding.
Tables 6 – 11 show that, in most instances, a
satisfactory degree of separation of calcite from the
ore can be achieved by the use of a strong magnetic
field, depending on feed particle size. This incurred
relatively small losses of nickel in the nonmagnetic
product according to the feed material. As seen in

Table 8 Table 10
Results of magnetic separation tests on the 2 + 1 mm size fraction Results of magnetic separation tests on the 1 mm size fraction of
of the ‘‘Kastoria’’ ore (high field intensity) the ‘‘Kastoria’’ ore (high field intensity)
Material Magnetic Nonmagnetic Feed Material Magnetic Nonmagnetic Feed
product product product product
wt.% 84.6 15.4 100 wt.% 94.6 5.4 100
Ni 1.85 0.47 1.64 Ni 1.98 0.61 1.90
CaO 10.97 32.49 14.28 CaO 11.73 32.91 12.88

Material Ni units Ni CaO CaO Material Ni units Ni CaO CaO

distribution units distribution distribution units distribution
(%) (%) (%) (%)
Magnetic 1.57 95.73 9.28 64.99 Magnetic 1.87 98.42 11.10 86.18
Nonmagnetic 0.07 4.27 5.00 35.01 Nonmagnetic 0.03 1.58 1.78 13.82
Feed 100.00 100.00 Feed 100.00 100.00
264 S. Agatzini-Leonardou et al. / Hydrometallurgy 74 (2004) 259–265

Table 11 7. Crushing to 4 mm of coarser fractions with

Results of magnetic separation tests on the 1 mm size fraction of nickel more than 0.5%.
the ‘‘Kastoria’’ ore (low field intensity)
8. Magnetic separation of the 4 + 1 mm fraction in
Material Magnetic Nonmagnetic Feed
a HGMS device.
product product
wt.% 95.3 4.7 100
The above scheme is expected to improve the
Ni 1.92 0.65 1.86
CaO 12.34 32.74 13.30 leaching behaviour of the serpentinic ore by lowering
the acid consumption during both agitation and heap
Material Ni units Ni CaO CaO leaching as well as improving the permeability of the
distribution units distribution ore heap.
(%) (%)
Magnetic 1.83 98.39 11.76 88.42
Nonmagnetic 0.03 1.61 1.54 11.58
Acknowledgements
Feed 100.00 100.00

The authors wish to express their gratitude to the

Tables 6– 11, nickel losses were 5%, at most, for a
feed particle size less than 4 mm. The respective
percentage CaO removal was about 37%, which was
considered adequate for the enhancement of the
permeability of this ore. On the other hand, magnetic
separation of the 1-mm fraction resulted in small
amounts of nonmagnetic products in the order of 5%
of the feed. Therefore, processing of this fraction
was considered unnecessary. The 10 + 4 mm frac-
tion should be ground to 4 mm in order to achieve
sufficient calcite liberation.
4. Conclusions
Based on the above experimental findings, the
following mineral processing scheme was devised
and applied for the ‘‘Kastoria’’ ore in order to prepare
a suitable sulphuric acid heap or agitation leaching
feed:
1. Classification of the 50-mm feed material by 16,
10, 4, and 1 mm size screens.
2. Crushing of the 50 + 16 mm ore in a jaw crusher
to the size of 16 mm.
3. Classification of the crusher product to the sizes of
stage 1.
4. Autogenous grinding of the 16 + 4 mm fraction
in a revolving drum.
5. Classification of the autogenous grinding product
to the sizes of stage 1.
6. Chemical analysis of the coarse size fractions for
possible rejection of those with less than 0.5% Ni.
European Commission, Directorate General XII, for
financial support according to contract no. BRE2-
CT94-1020 and, also, to G.M.M.S.A. LARCO for the
laterite samples provided.
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